CN1761612A - 部分氧化重整器－重整交换器结构 - Google Patents

部分氧化重整器－重整交换器结构 Download PDF

Info

Publication number
CN1761612A
CN1761612A CNA2004800068723A CN200480006872A CN1761612A CN 1761612 A CN1761612 A CN 1761612A CN A2004800068723 A CNA2004800068723 A CN A2004800068723A CN 200480006872 A CN200480006872 A CN 200480006872A CN 1761612 A CN1761612 A CN 1761612A
Authority
CN
China
Prior art keywords
reactor
reactor ejecta
ejecta
mixture
hydrocarbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2004800068723A
Other languages
English (en)
Other versions
CN100422072C (zh
Inventor
S·A·克内兹
A·马尔霍特拉
D·P·曼
M·J·范西克尔斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kellogg Brown and Root LLC
Original Assignee
Kellogg Brown and Root LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kellogg Brown and Root LLC filed Critical Kellogg Brown and Root LLC
Publication of CN1761612A publication Critical patent/CN1761612A/zh
Application granted granted Critical
Publication of CN100422072C publication Critical patent/CN100422072C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00018—Construction aspects
    • B01J2219/00024—Revamping, retrofitting or modernisation of existing plants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明公开了一种低耗能的氢的生产。重整交换器在具有改善的效率和减少了蒸汽排出的新制氢设备中、或者在现有的制氢设备中与部分氧化反应器并联，其制氢能力可以增加20－30％，而减少了制氢设备的蒸汽排出。

Description

部分氧化重整器-重整交换器结构
发明背景
本发明涉及使用部分氧化(POX)反应器和重整交换器生产合成气。
烃的重整是用于生产含氢合成气体的标准方法，该合成气例如用来生产氨或者甲醇。传统的POX反应器是非填充的(unpacked)、自由流动的非催化气体发生器，向其中供给预热的烃气和氧气，其任选带有温度调节器。然后使该部分氧化反应器的排出物骤冷或者冷却，一般到200-300℃，任选进行清洗以除去烟灰，并通常在高低温转换反应器中进行进一步转化，在该反应器中CO和蒸汽反应以形成额外的氢和CO2。人们特别希望得到具有高氢含量的合成气，用于氨或者其它合成方法，其中氢是来自合成气的主要反应物。在POX反应器进料中蒸汽与烃的重量比通常为0.1-5，在烃中氧与碳的原子比为0.6-1.6，并且反应时间为1-10秒。
POX反应器公开在例如美国专利US2,896,927；3,920,717；3,929,429；和4,081,253中，在此将它们全文引入作为参考。
在骤冷之前POX反应器产生很高温度，例如1100-1650℃的合成气排出物。这意味着大部分烃进料必须有效地被用作相当昂贵的燃料来预热进料，以及产生高压或中压蒸汽。然而，产生的蒸汽通常远远超过装置的需要量，因此必须将其排出，并且蒸汽常常有很小市场或者没有市场。
在本领域中需要一种改善使用POX反应器的制氢设备的效率并且将减少或消除蒸汽排出的方法。人们也常希望使得现有制氢设备制备的氢最大化或增加；然而POX反应器通常是能力有限的操作。POX反应器不易于扩大增产。
本发明通过把部分冷却的POX反应器工艺排出物供给重整交换器壳侧，以提供用于附加合成气生产的热量。所用重整交换器中自热重整器是已知的，例如参见LeBlanc的美国专利US 5,011,625和5,122,299以及Cizmer等人的US5,362,454，将所有文献全文在此引入作为参考。这些重整交换器可以以商标为KRES或Kellogg重整交换器体系商购获得。
发明概述
本发明在具有改善效率和减少蒸汽排出的新制氢设备中，或在现有制氢设备中，将重整交换器与部分氧化(POX)反应器并联使用。在一个实施方案中，制氢能力可以增加20-30％，而减少了从制氢设备排出的蒸汽。所得到的方法具有极低的能耗。
本发明提供用于制备合成气的方法。该方法包括：(a)在部分氧化反应器中用氧气把第一烃部分部分氧化，以产生第一反应器排出物；(b)冷却第一反应器排出物到650-1000℃的温度；(c)把第一反应器排出物供给重整交换器；(d)使第二烃部分和蒸汽经过重整交换器中的催化剂区段，以生成第二反应器排出物；(e)从催化剂区段排出第二反应器排出物，以与第一反应器排出物形成混合物；(f)使该混合物经过催化剂区段与之间接换热，以便冷却该混合物而加热催化剂区段；和(g)从重整交换器收集冷却的混合物。
冷却可以包括把水作为骤冷流体引入第一反应器排出物、间接换热、或水骤冷与间接换热相结合。可把间接换热用于预热交叉换热器中的第二烃部分。催化剂区段可以包括催化剂管。该方法还可以包括把第二烃部分供给重整交换器的管侧并使它经过该催化剂管，并且把冷却的第一反应器排出物供给重整交换器的壳侧进口。壳侧进口可以与催化剂管的出口相邻。该方法进一步地包括供给重量比为40∶60-95∶5的第一和第二烃部分。优选，第一和第二烃部分以40∶60-60∶40重量比供给(为了更有效地制造氢)，或80∶20-95∶5(如果想得到更多的CO)。
本发明还提供了一种合成气的生产设备。该设备包括：(a)用于用氧气把第一烃部分部分氧化以产生第一反应器排出物的部分氧化反应器装置；(b)用于把第一反应器排出物冷却到650-1000℃的温度的装置；(c)用于把第一反应器排出物供给重整交换器的装置；(d)用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的装置；(e)用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的装置；(f)用于使混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的装置；和(g)用于从重整交换器收集冷却的混合物的装置。
本发明进一步提供一种用于改进合成气工艺的方法，所述工艺包括用于把第一烃物流转化为第一反应器排出物的部分氧化反应步骤，用于冷却第一反应器排出物并用回收的热量生产蒸汽的热量回收步骤，以及用于回收冷却的反应器排出物并生产具有提高氢含量的合成气产品的下游处理步骤。改进包括：(a)用于把第一反应器排出物部分冷却到650-1000℃的温度的步骤；(b)用于把部分冷却的第一反应器排出物转入重整交换器的步骤；(c)用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的步骤；(d)用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的步骤；(e)用于使该混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的步骤；(f)用于把混合物从重整交换器送入热量回收步骤的步骤。
附图简述
图1是传统的现有技术POX方法的流程简图，其可以根据本发明的一个实施方案进行改进。
图2是根据本发明的一个实施方案的POX反应器和重整交换器集成在一起的合成气工艺的流程简图。
发明详述
本发明的改进装置具有图1表示的总体结构。把来自于管线2的脱硫天然气或其它烃与来自管线4的工艺蒸汽混合，并且把混合物在进料预热交换器(未显示)中预热。把预热的蒸汽-烃混合物经由管线6与氧气10送入一个POX反应器8(或多个POX反应器)中，并且将排放物收集在管线12中，用经由管线14注入的水骤冷，然后提供给下游加工段15，包括转换区段(高温，中温和/或低温转换器)，回收热量，除去CO2(例如，变压吸附或PSA)等等。生产出富氢的合成气流17。
根据如图2所示的本发明的一个实施方案来改进图1的装置，或构建新的装置。POX反应器8和管线2、4、6、10是常规的，如图1所述。将来自POX反应器8的在管线12内的工艺排出物用经由管线14的工艺用水骤冷到700-1100℃，优选750-1000℃，并且将混合物经由管线16供给重整交换器18的壳侧进口。除骤冷管线14之外还可以使用热交换器15，或用其代替骤冷管线14。可以使用热交换器15来预热进料流19。
把在管线19中预热的蒸汽和烃(其可以与管线2中的烃相同或不同)的混合物供给重整交换器18的管侧进口。混合物通过催化剂管20，以形成额外的含氢气体。将来自催化剂管20的出口孔的重整的气体与POX重整装置的排出物混合，并且使混合物通过催化剂管20外围进入壳侧出口，在此将其以常规的方式收集到管线22中。将管线22中的合并的合成气供给如图2的常规的下游加工段24，其包括转换转化器、用于回收热量的热交换单元，并进一步提纯，生产提纯的分子氢。在改进应用中，根据需要可以改造或扩大下游加工单元，以处理经由管线22供给的由添加的重整交换器18产生的额外的合成气。
通过POX反应器排出物的量和温度来满足重整交换器的热量需要。通常，通过管线19输入重整交换器18的进料越多，需要来自POX反应器排出物16的热量越多，以便维持催化剂管20中的通常吸热的重整反应。人们希望重整装置催化剂管排出气体的温度与该重整交换器18的结构材料所允许的温度一样高，例如在标准KRES设备中温度为750-1000℃。如果温度太低，在重整交换器18中会发生不充分的重整；而如果温度过高，则冶金因素将成问题。应当注意保证将温度选择得使金属粉尘化最小。
供给POX反应器8的烃的比例为总量的40-95％，而供给重整交换器18的比例为总烃进料的5-60％。人们希望POX反应器8和重整交换器18之间的进料分配可以使得POX反应器8必须产生合适量的热排出物，以提供重整交换器18所需的热量。分配到POX反应器8的进料为总量的40-60％，这有利于改善能源利用率和使制氢的速率最大，而将总烃进料的80-95％供给POX反应器有利于在合成气中产生更多CO。
通过实施例来说明本发明。将用于按照图2安装的集成的POX-重整交换器单元的基础工艺设计参数基于对图1的典型POX方法进行改进，管线16的物流组成和流速列在下表1中。表1还给出了根据图2结构进行改造的方法中所选物流的组成、性能和流速。
表1.POX反应器-重整交换器结构
   物流ID  ：组分   POX排放液管线16   催化剂管20入口物流组成，干   催化剂管20出口mol％   壳-侧出口管线22
  H2N2CH4ArCOCO2C2H6C3H8i-C4i-C5   62.350.660.660.1133.262.960.000.000.000.00   1.801.8094.400.000.100.201.200.300.100.10   73.790.473.040.0016.526.170.000.000.000.00   64.210.631.050.0930.543.490.000.000.000.00
  总流速，kmol/hrH2O，kmol/hr总流速，kmol/hr总流速，kg/hr压力(巴(a))温度(℃)   636.2153.2789.410,52832.4999.7   32.185.8117.92,07335.5308.8   123.550.3173.82,07332.4938.1   759.7203.5963.112,60132.1702.3
在仅使用POX反应器的基础情况下，由装置的重整区段产生的合成气将具有在管线16中的POX反应器排出物的组成和流速。依据本发明的该实施方案，将重整交换器与POX反应器并联使用，使在管线16中的排出物与从催化剂管20排出的气体混合以获得具有在管线22中的组成的合成气。该实施例表明，集成的POX-重整交换器方法可用于回收重整交换器中的废热并且使氢的生产提高20-25％。以这种方式将工艺热量用于附加的氢生产相应地减少了蒸汽的排出。
在上文中参考非限制性实施例说明了本发明，这些实施例仅是举例说明的目的。本领域技术人员在阅读了上文后，各种改进和变化都是显而易见的。所有这些改进和变化都落入由所附权利要求体现的本发明的范围和精神内。

Claims (21)

1.一种用于制备合成气的方法，包括：
在部分氧化反应器中用氧气把第一烃部分部分氧化，以产生第一反应器排出物；
冷却第一反应器排出物到650-1000℃的温度；
把第一反应器排出物供给重整交换器；
使第二烃部分和蒸汽经过重整交换器中的催化剂区段，以生成第二反应器排出物；
从催化剂区段排出第二反应器排出物，以与第一反应器排出物形成混合物；
使该混合物经过催化剂区段与之间接换热，以便冷却该混合物而加热催化剂区段；和
从重整交换器收集冷却的混合物。
2.根据权利要求1的方法，其中把水作为骤冷流体加入第一反应器排出物。
3.根据权利要求2的方法，其中冷却进一步包括间接换热。
4.根据权利要求3的方法，其中间接换热包括以交叉换热的方式加热第二烃部分。
5.根据权利要求1的方法，其中冷却包括换热。
6.根据权利要求5的方法，其中间接换热包括在交叉换热器中加热第二烃部分。
7.根据权利要求1的方法，其中催化剂区段包括催化剂管。
8.根据权利要求5的方法，其中把第二烃部分供给重整交换器的管侧并且使其通过催化剂管。
9.根据权利要求5的方法，其中把冷却的第一反应器排出物供给重整交换器的壳侧进口。
10.根据权利要求7的方法，其中壳侧进口与催化剂管的出口相邻。
11.根据权利要求1的方法，其中第一和第二烃部分以重量比40∶60-95∶5来供给。
12.根据权利要求1的方法，其中第一和第二烃部分以重量比40∶60-60∶40来供给。
13.根据权利要求1的方法，其中第一和第二烃部分以重量比95∶5-80∶20来供给。
14.一种用于生产合成气的设备，包括：
用于用氧气把第一烃部分部分氧化以产生第一反应器排出物的部分氧化反应器装置；
用于把第一反应器排出物冷却到650-1000℃的温度的装置；
用于把第一反应器排出物供给重整交换器的装置；
用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的装置；
用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的装置；
用于使混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的装置；和
用于从重整交换器收集冷却的混合物的装置。
15.一种用于改进包括以下步骤的合成气工艺的方法：用于把第一烃物流转化为第一反应器排出物的部分氧化反应步骤，用于冷却第一反应器排出物并用回收的热量生产蒸汽的热量回收步骤，以及用于回收冷却的反应器排出物并生产具有提高氢含量的合成气产品的下游处理步骤，该方法包括：
用于把第一反应器排出物部分冷却到650-1000℃的温度的步骤；
用于把部分冷却的第一反应器排出物转入重整交换器的步骤；
用于使第二烃部分与蒸汽经过重整交换器中的催化剂区段以生成第二反应器排出物的步骤；
用于把第二反应器排出物从催化剂区段排出以与第一反应器排出物形成混合物的步骤；
用于使该混合物经过催化剂区段与之间接换热以便冷却该混合物而加热催化剂区段的步骤；
用于将冷却的混合物从重整交换器送入热量回收步骤的步骤。
16.根据权利要求15的方法，其中把水作为骤冷流体加入第一反应器排出物。
17.根据权利要求11的方法，其中通过间接换热来冷却第一反应器排出物。
18.根据权利要求17的方法，其中在把第二烃部分供给重整交换器之前通过间接换热加热第二烃部分。
19.根据权利要求17的方法，其中把水加入第一反应器排出物。
20.根据权利要求11的方法，其中催化剂区段进一步包括催化剂管。
21.根据权利要求18的方法，其中把第二烃部分输入重整交换器的管侧进口。
CNB2004800068723A 2003-03-16 2004-03-16 部分氧化重整器-重整交换器结构 Expired - Lifetime CN100422072C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32001103P 2003-03-16 2003-03-16
US60/320,011 2003-03-16

Publications (2)

Publication Number Publication Date
CN1761612A true CN1761612A (zh) 2006-04-19
CN100422072C CN100422072C (zh) 2008-10-01

Family

ID=33029596

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004800068723A Expired - Lifetime CN100422072C (zh) 2003-03-16 2004-03-16 部分氧化重整器-重整交换器结构

Country Status (11)

Country Link
US (2) US7138001B2 (zh)
EP (1) EP1603831B1 (zh)
JP (1) JP4700603B2 (zh)
CN (1) CN100422072C (zh)
AU (1) AU2004221838B2 (zh)
BR (1) BRPI0406675A (zh)
CA (1) CA2510442C (zh)
EG (1) EG24088A (zh)
NZ (1) NZ542869A (zh)
RU (1) RU2338685C2 (zh)
WO (1) WO2004083115A2 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102099445A (zh) * 2008-07-18 2011-06-15 凯洛格·布朗及鲁特有限责任公司 催化部分氧化重整
CN102099284A (zh) * 2008-07-18 2011-06-15 凯洛格·布朗及鲁特有限责任公司 用于合成气加工的催化部分氧化重整
CN105836707A (zh) * 2016-05-17 2016-08-10 江苏省冶金设计院有限公司 非催化部分氧化-重整炉和利用其制备合成气的方法
CN108139072A (zh) * 2015-12-07 2018-06-08 托普索公司 用于转化步骤的入口温度的控制

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10359205B4 (de) * 2003-12-17 2007-09-06 Webasto Ag Reformer und Verfahren zum Umsetzen von Brennstoff und Oxidationsmittel zu Reformat
MY158899A (en) * 2004-10-04 2016-11-30 Shell Int Research Integrated process for hydrocarbon synthesis
NO20051895D0 (no) * 2005-04-19 2005-04-19 Statoil Asa Fremgangsmate for produksjon av elektrisk energi og CO2 fra et hydrokarbon rastoff
FR2890956B1 (fr) 2005-09-21 2008-04-18 Inst Francais Du Petrole Procede de production de gaz de synthese par vaporeformage et oxydation partielle
US20080016768A1 (en) 2006-07-18 2008-01-24 Togna Keith A Chemically-modified mixed fuels, methods of production and used thereof
US8197785B2 (en) * 2008-02-27 2012-06-12 Kellogg Brown & Root Llc Split flow contactor
CA2800508A1 (en) * 2010-05-26 2011-12-01 Gtlpetrol Llc Producing ammonia using ultrapure, high pressure hydrogen
US9388980B2 (en) 2011-12-15 2016-07-12 Kellogg Brown + Root LLC Systems and methods for gasifying a hydrocarbon feedstock
EP3538746A1 (en) 2016-11-09 2019-09-18 8 Rivers Capital, LLC Systems and methods for power production with integrated production of hydrogen
KR102651575B1 (ko) 2017-11-09 2024-03-27 8 리버스 캐피탈, 엘엘씨 수소 및 이산화탄소의 생산 및 분리를 위한 시스템들 및 방법들
KR20220020842A (ko) 2019-06-13 2022-02-21 8 리버스 캐피탈, 엘엘씨 추가 생성물들의 공동 발생을 구비하는 동력 생산
IT202000022336A1 (it) * 2020-09-22 2022-03-22 Bwe Patents S R L Processo di conversione di combustibile in correnti separate di anidride carbonica e di idrogeno
CA3238610A1 (en) 2021-11-18 2023-05-25 Rodney John Allam Apparatus for hydrogen production

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2929429A (en) 1955-06-03 1960-03-22 Firestone Tire & Rubber Co Tubeless tires having an air impervious graft polymer innerliner
US2896927A (en) * 1956-09-26 1959-07-28 Texaco Inc Gas and liquid contacting apparatus
GB944059A (en) * 1960-12-29 1963-12-11 Exxon Research Engineering Co Process for the production of ammonia synthesis feed gas
US3920717A (en) * 1973-03-26 1975-11-18 Texaco Development Corp Production of methanol
US3929429A (en) * 1974-09-26 1975-12-30 Texaco Inc Fuel gas from solid carbonaceous fuels
US4081253A (en) * 1976-12-10 1978-03-28 Texaco Development Corporation Production of purified synthesis gas and carbon monoxide
GB2163449B (en) * 1984-07-18 1988-06-02 Shell Int Research Production of gas mixtures containing hydrogen and carbon monoxide
DE3521304A1 (de) * 1985-06-13 1986-12-18 Linde Ag, 6200 Wiesbaden Verfahren zur erzeugung eines synthesegases
EP0334540B1 (en) * 1988-03-24 1993-10-20 Imperial Chemical Industries Plc Two-step steam-reforming process
US5122299A (en) * 1989-12-11 1992-06-16 The M. W. Kellogg Company Autothermal steam reforming process
US5011625A (en) * 1989-12-11 1991-04-30 The M. W. Kellogg Company Autothermal steam reforming process
JPH04310501A (ja) * 1991-04-03 1992-11-02 Mw Kellogg Co 自己熱式スチーム改質プロセス
DE4221837C1 (en) * 1992-07-03 1993-08-19 Uhde Gmbh, 4600 Dortmund, De Shrouded catalytic reformer tube - with partially enclosed gas mixing zone, for prodn. of synthesis gas
JPH06305702A (ja) * 1993-04-22 1994-11-01 Mitsubishi Gas Chem Co Inc ガス改質装置の起動方法
US5362454A (en) * 1993-06-28 1994-11-08 The M. W. Kellogg Company High temperature heat exchanger
US5358696A (en) * 1993-12-01 1994-10-25 Texaco Inc. Production of H2 -rich gas
US5560900A (en) * 1994-09-13 1996-10-01 The M. W. Kellogg Company Transport partial oxidation method
EP0834465B1 (en) * 1996-10-04 2000-07-19 Haldor Topsoe A/S Steam reforming process
US6005011A (en) * 1998-05-06 1999-12-21 The M. W. Kellogg Company Process for converting gas to liquids
JP4830197B2 (ja) * 2000-09-13 2011-12-07 トヨタ自動車株式会社 燃料改質装置
US6855272B2 (en) * 2001-07-18 2005-02-15 Kellogg Brown & Root, Inc. Low pressure drop reforming exchanger
US20030162846A1 (en) * 2002-02-25 2003-08-28 Wang Shoou-L Process and apparatus for the production of synthesis gas

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102099445A (zh) * 2008-07-18 2011-06-15 凯洛格·布朗及鲁特有限责任公司 催化部分氧化重整
CN102099284A (zh) * 2008-07-18 2011-06-15 凯洛格·布朗及鲁特有限责任公司 用于合成气加工的催化部分氧化重整
CN102099284B (zh) * 2008-07-18 2014-10-29 凯洛格·布朗及鲁特有限责任公司 用于合成气加工的催化部分氧化重整
CN102099445B (zh) * 2008-07-18 2015-01-28 凯洛格·布朗及鲁特有限责任公司 催化部分氧化重整
CN108139072A (zh) * 2015-12-07 2018-06-08 托普索公司 用于转化步骤的入口温度的控制
CN105836707A (zh) * 2016-05-17 2016-08-10 江苏省冶金设计院有限公司 非催化部分氧化-重整炉和利用其制备合成气的方法
CN105836707B (zh) * 2016-05-17 2018-07-17 江苏省冶金设计院有限公司 非催化部分氧化-重整炉和利用其制备合成气的方法

Also Published As

Publication number Publication date
EP1603831B1 (en) 2012-04-18
RU2005131948A (ru) 2006-02-10
AU2004221838A1 (en) 2004-09-30
BRPI0406675A (pt) 2005-12-20
NZ542869A (en) 2009-04-30
US20040177555A1 (en) 2004-09-16
US7138001B2 (en) 2006-11-21
AU2004221838B2 (en) 2010-03-25
JP4700603B2 (ja) 2011-06-15
US20080047197A1 (en) 2008-02-28
JP2006520316A (ja) 2006-09-07
EP1603831A2 (en) 2005-12-14
WO2004083115A3 (en) 2005-01-27
EP1603831A4 (en) 2009-08-26
CA2510442C (en) 2011-09-13
CA2510442A1 (en) 2004-09-30
RU2338685C2 (ru) 2008-11-20
CN100422072C (zh) 2008-10-01
EG24088A (en) 2008-05-21
WO2004083115A2 (en) 2004-09-30

Similar Documents

Publication Publication Date Title
CN100422072C (zh) 部分氧化重整器-重整交换器结构
CN100564495C (zh) 制氢用自热转化器-转化交换器布置
EP0522744B1 (en) Synthesis gas production
CN101191084B (zh) 以甲烷重整方式利用煤气化显热的多联产能源方法及系统
CN101274744B (zh) 具有再循环的催化蒸汽重整
CN100526273C (zh) 以焦炉气为原料一体化生产液氨和甲醇和/或二甲醚的方法
CA2435960A1 (en) Hydrogen enrichment scheme for autothermal reforming
CN105377798A (zh) 使用基于氧转运膜的重整系统生产甲醇的方法和系统
CN106145035A (zh) 制氢方法
US20080237090A1 (en) Process and system for redcuing the olefin content of a hydrocarbon feed gas and production of a hydrogen-enriched gas therefrom
CN102498060A (zh) 用于生产甲醇的联合转化方法
CN101985574B (zh) 一种利用合成气制备天然气的工艺方法
CN110877897B (zh) 具有co调节的双产物h2和co制备
CN212237215U (zh) 自热净化炉和变换反应及热回收装置
CN106564861A (zh) 一种高效回收烃类蒸汽转化制氢过程中转化气能量的工艺
US20240228274A1 (en) Process and plant for the production of synthesis gas and generation of process condensate
CN212451325U (zh) 一种低氢高碳富甲烷气的处理利用系统
EP1888456B1 (de) Autothermer reformer
EP2865640A1 (en) Water purification using energy from a steam-hydrocarbon reforming process
CN114075461A (zh) 一种低氢高碳富甲烷气的处理利用工艺及系统
CN115784151A (zh) 一种高co浓度工业尾气的中温绝热变换工艺
CN1076390C (zh) 一种提高一氧化碳气体热质的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20081001